Abstract. The construction of valuable complex molecules from readily available chemical precursors is a central goal in synthesis. Bioactive small molecules (including pharmaceuticals and agrochemicals) are especially valuable because they influence human health and global food production. Our overall research goal is to develop new patterns in chemical reactivity that can be utilized in the solution of many diverse and impactful problems. Our lab has developed a family of radical anion-based processes that selectively activate heteroaromatic substrates for selective coupling with a range of different olefin types. Here we seek to extend this mechanistic strategy to the construction of many different valuable compound classes. In Aim 1, we propose a new strategy for the preparation of valuable fluorinated compounds through the cleavage of very strong C?F bonds (in aryl trifluoromethyl groups). We present a number of different ways that activation of these substrates by radical-anion formation could be utilized in bond-forming processes. Aim 2 seeks to utilize aryl and heteroaryl radical anions in the formation of privileged pharmacophores. In Aim 3, we describe a novel strategy for the synthesis of unnatural peptides.